Primary amines covalently bonded to the surface of poly(dimethylsiloxane) were obtained by hydrosilylation grafting of aminopropyl vinyl ether to Si-H groups formed during argon plasma treatment. The amine groups were derivatized using pentafluorobenzaldehyde and characterized by X-ray photoelectron spectroscopy. The graft yield was about 3% grafted molecules within the depth of the analysis. The terminal aldehyde groups of diazotized heparin was also coupled to the primary amines. This led to a silicone elastomer with covalently bonded heparin which was expected to be hydrolytically stable. This method of bonding primary amines to the surface of silicone elastomers and the subsequent coupling of aldehyde-containing molecules is a promising way of obtaining novel biomaterials.